Thioureido sulfonanilide compositions

ABSTRACT

New compounds corresponding to the generic formula:   WHEREIN R can be selected from lower alkyl, lower haloalkyl, phenyl, substituted phenyl wherein said substituents can be selected from halogen and lower alkyl; R1 can be selected from lower alkyl, lower alkoxy and lower thioalkyl. The compounds are useful fungicides and biocides.

' nited States Patent Mihailovski Dec. 16, 1975 THIOUREIDO SULFONANILIDE COMPOSITIONS Primary Examiner-Lewis Gotts Assistant Examiner-D. R. Phillips [75] Inventor. giiigmder Mihallovskl, Berkeley, Attorney, Agent, or Firm Daniel C. Block [73] Assignee: Stauffer Chemical Company, [57] ABSTRACT westport Conn- New compounds corresponding to the generic for- 22 Filed: June 12, 1974 mula:

[21] Appl. No.: 478,490

Related U.S. Application Data NHI-SOQ R [62] Division of Ser. No: 217,697, Dec. 29, 1971, Pat. No. NH-C -NH-C -R [52] U.S. Cl 260/552 R [51] Int. Cl. C07C 143/833 [58] Field of Search ..-260/552 R wherem R can be Selected from lower alkyl, lower oalkyl, phenyl, substituted phenyl wherein said substit- [56] References Cited uents can be selected from halogen and lower alkyl; R can be selected from lower alkyl, lower alkoxy and 3 49 9 :V f lsATENTs 260,552 R lower thioalkyl. The compounds are useful fungicides eyer e a 3,803,227 4/1974 Joos et al and bocldes' 3,832,384 8/1974 Mihailovski 260/552 R 9 Claims, N0 Drawings THIOUREIDO SULFONANILIDE COMPOSITIONS This is a division of application Ser. No. 217,697 filed Dec. 29, 1971 now US. Pat-No. 3,832,384.

DESCRIPTION OF THE INVENTION This invention is directed to a novel group of compounds which may be generally described as thioureido sulfonanilides which are highly active fungicides and stirring 2.6 g. (0.020 mole) ethoxycarbonyl isothiocyabiocides. The compounds of the present invention are represented by the generic formula:

so R

u H 1 S .0

wherein R can be selected from lower alkyl, lower haloalkyl, phenyl, substituted phenyl wherein said substituents can be selected from halogen and lower alkyl; R can be selected from lower alkyl, lower alkoxy and lower thioalkyl.

The above compounds can be prepared by treating a 2-aminoalkylsulfonanilide or Z-aminoarylsulfonanilide with an appropriate carbonyl isothiocyanate in an inert solvent such as acetone or the like. The products form rapidly and can be isolated in good purity.

In order to illustrate the merits of the present invention the following examples are provided.

EXAMPLE 1.

Preparation of 2-[ 3 Ethoxycarbonyl )-thioureido benzenesulfonanilide To 5.0 g. (0.020 mole) of 2-aminobenzenesulfonanilide dissolved in 30 ml. of acetone were added with TABLE I -so R @NH 2 NH-C-NH- R M ii 1 s o ComEouncI No nate dissolved in 10 ml. of acetone. This mixture was stirred for 16 hours at room temperature and the precipitated solid was filtered to yield 6.3 g. of 2-[3'- ethoxycarbonyl)-thioureido]benzenesulfonanilide,

m.p. 180-181C. (dec.). Yield, 83% of theory.

EXAMPLE 2 Preparation of 2-[ 3 Ethoxycarbonyl thioureido ]-methanesulfonanilide FUNGICIDE TESTING PROCEDURES A. Foliar Preventative Sprays 1. Bean Rust Thechemicals are dissolved in an appropriate solvent and diluted with water containing several drops of Tween 20, a wetting agent. Test concentrations, ranging from 1000 ppm downward, are sprayed to runoff on the primary leaves of pinto beans (Phaseolus vulgaris L.). After the leaves are dried, they are inoculated with a water suspension of spores of the bean rust fungus i (Uromyces phaseoli Arthur) and the plants are placed in an environment of humidity for 24 hours. The

CH CH Compound No. i

35 CH --CH H2')-3CH3 37 -c CI CH 38 3 2 CH plants are then removed from the humidity chamber and held until disease pustules appear on the leaves. Effectiveness is recorded as the lowest concentration, in ppm which will provide 50% reduction in pustule formation as compared to untreated inoculated plants. 2. Bean Powdery Mildew Test chemicals are prepared and applied in the same manner as for the bean rust test. After the plants are dry, the leaves are dusted with spores of the powdery mildew fungus (Erysiphe polygoni De Candolle) and the plants are retained in the greenhouse until the fungal growth appears on the leaf surface. Effectiveness is recorded as the lowest concentration, in ppm, which will provide 50% reduction in pustule formation as compared to untreated inoculated plants.

3.. Tomato Early Blight Test chemicals are prepared and applied in the same manner as the bean rust and powdery mildew tests except that 4-week old tomato (Lycopersicon esculentum) plants are utilized as the host plant. When the leaves are dry, they are inoculated with a water suspension of spores of the early blight fungus (Alternaris solani Ellis and Martin) and placed in an environment of 100% humidity for 48 hours. The plants are then removed from the humidity chamber and held until disease lesions appear on the leaves. Effectiveness is recorded as the lowest concentration, in ppm, which will provide 50% reduction in number of lesions formed as compared to untreated inoculated plants. B. Tube Systemic Test 1. Bean Rust The chemicals are dissolved in an appropriate solvent and diluted with tap water to a series of descending concentrations beginning at 50 ppm. Sixty ml. of each concentration are placed in a test tube. A pinto bean OCH CH OCH CH -OCH CH OCH C C OCH CH CH2 H plant is placed in each tube and supported with a piece of cotton so that only the roots and lower stem are in contact with the test solution. Forty-eight hours later the bean leaves are inoculated with a water suspension of spores of the bean rust fungus and placed in an environment with 100% humidity for 24 hours. The plants are then removed from the humidity chamber and maintained in the greenhouse until the disease pustules appear on the leaves. Effectiveness is recorded as the lowest concentration, in ppm, which will provide 50% reduction in pustule formation as compared to untreated, inoculated plants.

2. Bean Powdery Mildew Test chemicals are prepared and applied in the same manner as for the bean rust systemic test. After 2 days the leaves are dusted with spores of the powdery mildew fungus and maintained in the greenhouse until mycelial growth appears on the leaf surfaces. Effectiveness is recorded as the lowest concentration, in ppm, which will provide a 50% reduction in mycelial growth on the leaf surface as compared to untreated, inoculated plants.

C. Systemic Soil Drench 1. Bean Rust Pinto beans are grown in l-pint ice cream cartons, each containing 1 lb. of soil. Aliquots of the toxicant, dissolved in an appropriate solvent, are diluted with 25 m1. of water and drenched onto the soil surface. Two days later the bean leaves are inoculated with a water suspension of spores of the rust fungus, and the plants are placed in an environment with 100% humidity for 24 hours. The plants are then removed from the humidity chamber and maintained in the greenhouse until the pustules appear on the leaves. Effectiveness is recorded as the minimum concentration, in ppm per lb. of soil,

TABLE II Com- Foliar Spray Tube Systemic Soil Drench pound No. Rust Mildew Tomato Blight Rust Mildew Rust Mildew 2s 1o00 10o0 which will provide 50% reduction in number of pus- TABLE IH tules as compared to untreated inoculated plants. 1 C

ompound 2. Bean Powdery Mildew No. A.n. P.i. 13.6. 8.21. The bean plants and chemicals are prepared and l (50) 5) 50 applied as in the rust systemic soil drench test. After 40 2 50 50 50 ten days, the bean leaves are dusted with spores of the Z :28 3 :28; powdery mildew fungus and maintained in the green- 5 50 (5) 50 house until the mycelial growth appears on theleaf 3 8 8 28 55 surface. Effectiveness is recorded as the minimum con- 8 :2 50) centration, in ppm per lb. of soil, which will provide 9 50) 50 50 50% reduction in mycelial growth on the leaf surface in i? :23 8 :28 comparison to untreated, v inoculated plants. 12 50 (25) 50 50 13 50 50 50 50 BIOCIDE TESTING PROCEDURES 14 50 25 50 50 5O 15 50 50 50 50 Tubes of sterilized nutrient and malt extract broth :9, Z28 :28 :28 :28 are prepared. Aliquots of the toxi'cant, dissolved in an 18 50 50 50 50 appropriate solvent, are injected through the stopper, 3 :28 :28 p :28 into the broth, to prov1de concentrations ranging from 21 50 50 1 50 50 50 ppm downward. The test organisms consist of two 22 50 50 50 50 fun As A 23 50 5 1 50 50 g1, perg1 us mger .n.) van Tieghem and Penzczl- 24 50 50 50 50 lzum ltalzcum (P.1.) Wehmer, and two bacteria, Escher- 25 ichia coli (E.c.) Migula and Staphylococcus aureus 5? :28 55()0 :28 if;

(S.a.) Rosenbach. Three drops of a spore suspension of 28 50 10 50 50 each of the fungi are injected into the tubes of malt i3 :28 :28 broth and three drops of the bacteria are injected into 31 5 50 50 50 25 the nutrient broth. One week later the growth of each :28 :28 :gg igg organism 1s observed and efi'ectiveness of the chemical 34 50 50 50 50 is recorded as the lowest concentration in ppm which 35 36 50 50 50 2 provides 50% inhibit on of growth as compared to un- 25 50 50 treated inoculated tubes. The results of these tests are tabulated in Table III.

( partial control The compounds of this invention are generally embodied into a form suitable for convenient application. For example, the compounds can be embodied into pesticidal composition which are provided in the form of emulsions, suspensions, solutions, dusts and aerosol sprays. In general, such compositions will contain, in addition to the active compound, the adjuvants which are found normally in pesticide preparations. In these compositions, the active compounds of this invention can be employed as the sole pesticide component or they can be used in admixture with other compounds having similar utility. The pesticide compositions of this invention can contain, as adjuvants, organic solvents, such as sesame oil, xylene range solvents, heavy petroleum, etc.; water; emulsifying agents; surface active agents; talc; pyrophyllite; diatomite; gypsum; clays; propellants, such as dichlorodifluoromethane, etc. If desired, however, the active compounds can be applied directly to feedstuffs, seeds, etc. upon which the pests feed. When applied in such a manner, it will be advantageous to use a compound which is not volatile. In connection with the activity of the presently disclosed pesticidal compounds, it should be fully understood that it is not necessary that they be active as such. The purposes of this invention will be fully served if the compound is rendered active by external influences, such as light or by some physiological action which occurs when the compound is ingested into the body of the pest.

The precise manner in which the pesticidal compositions of this invention are used in any particular instance will be readily apparent to a person skilled in the art. Generally, the active pesticide compound will be embodied in the form of a liquid composition; for example, an emulsion, suspension, or aerosol spray. While the concentration of the active pesticide in the present compositions can vary within rather wide limits, ordinarily the pesticide compound will comprise not more than about 15.0% by weight of the composition. Preferably, however, the pesticide compositions of this invention will be in the form of solutions or suspensions containing about 0.1 to 1.0% by weight of the active pesticide compound.

What is claimed is:

1. Compounds corresponding to the generic formula: 4

wherein R can be selected from lower alkyl, lower haloalkyl, phenyl, substituted phenyl wherein said substituents can be selected from halogen and lower alkyl; and R is lower alkyl.

2. A compound as set forth in claim 1 wherein R is CI-l and R, is CI-I CH 3. A compound as set forth in claim 1 wherein R is and R is 4. A compound as set forth in claim 1 wherein R is and R is CI-I CH 5. A compound as set forth in claim 1 wherein R is CI-I CII and R is CH CH 6. A compound as set forth in claim 1 wherein R is and R is -CH 9. A compound as set forth in claim 1 wherein R is CH2CH2CH3 and R1 IS 

1. COMPOUNDS CORRESPONDING TO THE GENERIC FORMULA:
 2. A compound as set forth in claim 1 wherein R is -CH3 and R1 is -CH2CH3.
 3. A compound as set forth in claim 1 wherein R is
 4. A compound as set forth in claim 1 wherein R is
 5. A compound as set forth in claim 1 wherein R is -CH2CH3 and R1 is -CH2CH3.
 6. A compound as set forth in claim 1 wherein R is
 7. A compound as set forth in claim 1 wherein R is -CH3 and R1 is -CH3.
 8. A compound as set forth in claim 1 wherein R is
 9. A compound as set forth in claim 1 wherein R is -CH2CH2CH3 and R1 is -CH3. 